含十二烷基苯磺酸及其有机金属盐掺杂物之奈米管聚苯胺研究.doc

中文摘要 本研究主要是利用自組裝的乳化聚合方式合成聚苯胺奈米管，但不同於以往以十二烷基苯磺酸(Dodecylbenzenesulfonic acid, DBSA) 作為界面活性劑，而改用含十二烷基苯磺酸有機鋅鹽 (Zn(DBSA)2 )，而以往是將 Zn(DBSA)2 與聚苯胺直接混煉，藉由鋅離子與聚苯胺主鏈上的氮強烈的物理吸引力，形成自我組裝的梳狀結構 (comb-shaped)，並提升聚苯胺主鏈上之共軛度。而本研究是藉由其中二價鋅離子錯合兩個十二烷基苯磺酸根，使其有具兩個親油端分子，希望藉由這樣的界面活性劑去影響其合成後的形態，使其易於形成分支管 (branched nanotubes) 形態之奈米聚苯胺，並希望藉著聚苯胺的還原能力將鋅離子還原，使金屬鋅可以直接生長在奈米管上，以增加其導電度及應用性。 初步先以苯胺單體及聚苯胺與硝酸鋅水溶液混合，發現不如預期可以將鋅還原。合成時依照以往以 DBSA 作為界面活性劑合成聚苯胺之條件，發現所合成出之形態為纖維聚集之珊瑚狀狀態。透過改變合成條件，如合成溫度及合成時之pH值，並藉由穿透式電子顯微鏡(TEM)及掃瞄式電子顯微鏡(SEM)的分析，確定所合成出的聚苯胺為奈米管形態，並在其中幾組樣品中發現有類似分支管的形態產生。但Zn(DBSA)2 作為界面活性劑在聚合成聚苯胺奈米管的合成機制中扮演的角色仍須更進一步詳盡的研究及探討。 英文摘要 A nanotubular polyaniline was prepared by self-assembly emulsion polymerization with emulsifier “ dedcylbenzenesulfonic acid organic zinc salt, Zn(DBSA)2 ”. Formerly, Zn(DBSA)2 was used for both plasticizing doped polyaniline by blending and improving the conjugation chain length of polyaniline. This study took advantage of a couple of hydrophobic tail of Zn(DBSA)2 to influence the micelle configuration which led to change of the resultant polymers. In the meantime, we also expected to reduce the zinc ions into zinc metals by polyaniline to improve the conductivity of polyaniline. However, we found the zinc ions couldn’t be easily reduced by either polyaniline or aniline monomer. And then, we adopted the Zn(DBSA)2 in the polymerization of polyaniline as part of the emulsifiers with “ dedcylbenzenesulfonic acid, DBSA ”. We observed the obtained polyaniline was coral like. Via the alternation of the reaction temperature and pH value, and analysis by SEM and TEM, we successfully prepared a nanotubular polyaniline, and we also found branching nanotube. But the role that Zn(DBSA)2 plays on mechanism of nanotubular polyaniline polymerization still needs further discussion. 目錄 摘要 I ABSTRACT II 目錄 III 表目錄 IV 圖目錄 IV 第一章 緒論 1 1-1 前言 1 1-2 研究動機 3 第二章 文獻回顧 5 2-1 導電高分子發展過程 5 2-1-1 導電性高分子種類 9 2-1-2 導電高分子奈米管 11 2-2 聚苯胺(Polyaniline) 13 2-2-1 奈米管聚苯胺之合成 17 2-2-2 聚苯胺之性質 22 2-2-2-1 聚苯胺紅外線光譜分